Vapor deposition precursor compounds and process of use
Provided is a plasma enhanced atomic layer deposition (PEALD) process for depositing etch-resistant SiOCN films. These films provide improved growth rate, improved step coverage and excellent etch resistance to wet etchants and post-deposition plasma treatments containing O 2 and NH 3 co-reactants. This PEALD process relies on one or more precursors reacting in tandem with the plasma exposure to deposit the etch-resistant thin-films of SiOCN. The films display excellent resistance to wet etching with dilute aqueous HF solutions, both after deposition and after post-deposition plasma treatment(s). Accordingly, these films are expected to display excellent stability towards post-deposition fabrication steps utilized during device manufacturing and build.
1. A process for the vapor deposition of a silicon oxycarbonitride film onto a microelectronic device surface in a reaction zone, which comprises sequentially introducing into said reaction zone reactants chosen from (i) at least one silylamine, (ii) at least one oxiranyl silane, wherein (i) and (ii) are introduced in either order, and (iii) a reducing gas in plasma form, with purging of each reactant prior to exposing the film to the next reactant,
wherein the silylamine has two silicon atoms per molecule and the oxiranyl silane selected from:
compounds of the formula:
wherein each R is independently chosen from C 1 -C 4 alkyl, and x is zero or 1;
compounds of the formula
wherein each R 1 is independently chosen from a C 1 -C 4 alkyl group or a group of the formula
wherein each R 3 is independently chosen from hydrogen or C 1 -C 4 alkyl; and
wherein each R 2 is independently chosen from hydrogen or C 1 -C 4 alkyl.
2. The process of claim 1 , wherein the silicon oxycarbonitride film so formed exhibits an ashing damage difference of only about 4 angstroms over a silicon nitride reference sample when exposed to oxygen plasma at 100 Watts for 60 seconds.
3. The process of claim 1 , wherein the silylamine is
4. The process of claim 1 , wherein the oxiranyl silane is
5. The process of claim 1 , wherein the oxiranyl silane is
6. The process of claim 1 , wherein the oxiranyl silane is
7. The process of claim 1 , wherein the oxiranyl silane is chosen from compounds of the formula:
wherein each R is independently chosen from C 1 -C 4 alkyl, and x is zero or 1.
8. The process of claim 1 , wherein the oxiranyl silane is chosen from compounds of the formula
wherein each R 1 is independently chosen from a C 1 -C 4 alkyl group or a group of the formula
9. The process of claim 1 , wherein the oxiranyl silane is chosen from
wherein each R 3 is independently chosen from hydrogen or C 1 -C 4 alkyl.
10. The process of claim 1 , wherein the oxiranyl compound is chosen from
wherein each R 2 is independently chosen from hydrogen or C 1 -C 4 alkyl.
11. A process for depositing a silicon oxycarbonitride film on a microelectronic device surface in a reaction zone under atomic layer deposition conditions, which comprises sequentially introducing into said reaction zone:
a. a silylamine chosen from:
b. followed by purging said reaction zone with an inert gas;
c. followed by introducing into said reaction zone an oxiranyl silane chosen from
compounds of the formula:
wherein each R is independently chosen from C 1 -C 4 alkyl, and x is zero or 1; and
compounds of the formula
wherein each R 1 is independently chosen from a C 1 -C 4 alkyl group or a group of the formula
wherein each R 3 is independently chosen from hydrogen or C 1 -C 4 alkyl; and
wherein each R 2 is independently chosen from hydrogen or C 1 -C 4 alkyl;
d. followed by purging said reaction zone with an inert gas;
e. followed by introducing into said reaction zone a reducing gas in plasma form;
f. followed by purging said reaction zone with an inert gas; and
repeating steps a. through f. until a film of a desired thickness has been deposited.
12. A process for depositing a silicon oxycarbonitride film on a microelectronic device surface in a reaction zone under atomic layer deposition conditions, which comprises sequentially introducing into said reaction zone:
a. an oxiranyl silane chosen from
compounds of the formula:
wherein each R is independently chosen from C 1 -C 4 alkyl, and x is zero or 1; and
compounds of the formula
wherein each R 1 is independently chosen from a C 1 -C 4 alkyl group or a group of the formula
wherein each R 3 is independently chosen from hydrogen or C 1 -C 4 alkyl; and
wherein each R 2 is independently chosen from hydrogen or C 1 -C 4 alkyl;
b. followed by purging said reaction zone with an inert gas;
c. followed by introducing into said reaction zone a silylamine chosen from:
d. followed by purging said reaction zone with an inert gas;
e. followed by introducing into said reaction zone a reducing gas in plasma form;
f. followed by purging said reaction zone with an inert gas; and
repeating steps a. through f. until a film of a desired thickness has been deposited.